Water-insoluble pyrazolone azo dyestuffs

ABSTRACT

WATER-INSOLUBLE DYESTUFFS ARE PROVIDED HAVING THE FORMULA:   A,(D1-(N=N-B(-Z)(-Z&#39;&#39;))M-N=N-),(Y-CO-X-OOC-)-BENZENE   OR THE FORMULA   A,(D2-(N=N-B(-Z)(-Z&#39;&#39;))M-N=N-),(Y-COO-X-OOC-)-BENZENE   IN WHICH B REPRESENTS A P-PHENYLENE OR P-NAPHTHYLENE RADICAL LINKED TO THE NITROGEN ATOMS, M REPRESENTS THE NUMBERS 0 OR 1, X REPRESENTS AN ALKYLENE RADICAL HAVING UP TO 4 CARBON ATOMS, Z AND Z&#39;&#39; EACH REPRESENT A HYDROGEN OR HALOGEN ATOM OR AN ALKYL, ALKOXY, OR ACYLAMINO GROUP HAVING UP TO 4 CARBON ATOMS, Y REPRESENTS AN ALIPHATIC, ARYLALIPHATIC, AROMATIC OR HETEROCYCLIC RADICAL, D1 REPRESENTS THE RESIDUE OF A COUPLING COMPOUND OF THE BENZENE, DIPHENYLENEOXIDE, INDAZOLE, COUMARIN, ACETYLACETARYLIDE, PYRAZOLONE OR HYDROXY-QUINOLINE SERIES, D2 REPRESENTS THE RESIDUE OF A COUPLING COMPOUND OF THE BENZENE, DIPHENYLENE-OXIDE, INDAZOLE, COUMARIN, ACETYLACETARYLIDE, HYDROXYQUINOLINE, 1 - PHENYL-3-METHYL-PYRAZOLONE OF 1-PHENYL-3CARBONAMIDOPYRAZOLONE SERIES, THE NUCLEI A, B, D1, D2 AND Y CONTAINING NO SOLUBILISING ACID GROUPS. THESE DYESTUFFS ARE USEFUL FOR THE COLOURATION OF HYDROPHOBIC TEXTILE MATERIALS AND MAY BE PREPARED FROM NOVEL DIAZOTISABLE BASES OF THE GENERAL FORMULA:   Y-COO-X-OOC-ANILINE   IN WHICH X, Y, Z AND Z&#39;&#39; ARE AS DEFINED ABOVE. THE SHADES OBTAINED ARE REMARKABLY FAST TO THERMAL FIXATION, SUBLIMATION, CREASING, COMBUSTION GASES, OVERDYEING, DRY CLEANING, CHLORINE AND WET TESTS. THE RESERVE OF NATURAL FIBRES AND THE DISCHARGEABILITY ARE GOOD. THE FASTNESS TO LIGHT IS REMARKABLE EVEN WITH LIGHT SHADES AND THE DYESTUFFS RESIST BOILING AND REDUCTION AT TEMPERATURES BETWEEN 80* C. AND 220* C.

United States Patent 5 5 Int. Cl. C09b 29/38 31/14; D0611 3/00 US. Cl. 260-163 3 Claims ABSTRACT OF THE DISCLOSURE Water-insoluble dyestuffs are provided having the foror the formula:

in which B represents a p-phenylene or p-naphthylene radical linked to the ntirogen atoms, m represents the numbers 0 or 1, X represents an alkylene radical having up to 4 carbon atoms, Z and Z each represent a hydrogen or halogen atom or an alkyl, alkoxy, or acylamino group having up to 4 carbon atoms, Y represents an aliphatic, arylaliphatic, aromatic or heterocyclic radical, D represents the residue of a coupling compound of the benzene, diphenyleneoxide, indazole, coumarin, acetylacetarylide, pyrazolone or hydroxy-quinoline series, D represents the residue of a coupling compound of the benzene, diphenylene-oxide, indazole, coumarin, acetylacetarylide, hydroxyquinoline, 1 phenyl-3-methyl-pyrazolone or 1-phenyl-3- carbonamidopyrazolone series, the nuclei A, B, D D and Y containing no solubilising acid groups. These dyestuffs are useful for the colouration of hydrophobic textile materials and may be prepared from novel diazotisable bases of the general formula:

in which X, Y, Z and Z are as defined above. The shades obtained are remarkably fast to thermal fixation, sublimation, creasing, combustion gases, overdyeing, dry cleaning, chlorine and wet tests. The reserve of natural fibres and the dischargeability are good. The fastness to light is remarkable even with light shades and the dyestuffs resist boiling and reduction at temperatures between 80 C. and 220 C.

The present invention relates to new intermediates products and to new water-insoluble monoor disazodyestuffs, which are particularly interesting for the colouration of hydrophobic textile materials, especially textile materials based on aromatic polyesters.

Patented May 16, 1972 These new dyestuffs may be represented by the general formulae:

in which B represents a paraphenylene or paranaphthylene radical linked to the nitrogen atoms, m represents the number 0 or 1, X represents an alkylene radical having up to 4 carbon atoms, Z and 2' each represent a hydrogen or halogen atom or an alkyl, alkoxy, or acylamino group having up to 4 carbon atoms, Y represents an aliphatic, arylaliphatic, aromatic or heterocyclic radical, D represents the residue of a coupling compound of the benzene, diphenylene oxide, indazole, coumarin, acetylacetarylide, pyrazolone, or hydroxyquinoline series, D represents the residue of a coupling compound of the benzene, diphenyl ene oxide, indazole, coumarin, acetylacetarylide, hydroxyquinoline, 1 phenyl-3-methylpyrazolone or 1-phenyl3- carbonamido-pyrazolone series, the nuclei A, B, D D and Y containing no solubilising acid groups.

The residue Y can be, for example a methyl, ethyl, isopropyl, trifluoromethyl, acetylethyl, benzyl, 2',4'-dichloro-phenoxyethyl, styryl, phenyl, chlorophenyl, toluyl, methoxyphenyl, B-furylvinyl or pyridinyl group.

The residues D and D can be substituted, for example, by halogen atoms, alkyl, alkoxy, trifiuoromethyl, alkylsulphonyl, alkylcarbonyl, alkoxycarbonyl, hydroxy, acylamino, N-alkyl acylamino, aminocar-bonyl, aminosulphonyl, alkylaminocarbonyl, alkylaminosulphonyl groups.

The dyestuffs of Formulae Ia and lb in which m represents zero :may be prepared, for example by diazotising a base of the general formula:

and coupling the diazo derivative with a compound D H or D H possessing a free coupling position, the significance of X and Y and the possible substituents of D and D being as defined above.

The dyestuffs of Formulae I in which m is equal to 1 may be prepared, for example, by coupling the diazo derivative of a base of Formula II with an amine of formula diazotising the amino-monoazo dyestuff thus obtained and coupling with a coupling compound D H or D H.

The dyestuffs of Formula I may also be prepared by acylating dyestuffs of the formula:

CO-O-X-OH (III) by means of an acid chloride YCOCl in the presence of an acid-absorbing agent, possibly in an inert diluent, or by means of an acid anhydride (YCO) O. This method can only be carried out, however, if the dyestuff of Formula III does not contain any other acylable group than the OH group carried by the radical X.

The bases of Formula II may themselves be prepared, for example, by the following processes:

(1) starting from a benzoyl nitrochloride by condensation with an acylglycol of formula and reduction of the nitro group or by condensation with a glycol, acylation by means of an acid chloride Y-COCl or an acid anhydride (YCO) O and reduction of the nitro group,

or (2) starting from a nitrobenzoic acid by esterification by means of an acylglycol and reduction of the nitro group by esterification by means of a glycol, acylation as before and reduction of the nitro group or by oxyalkylation, acylation as before and reduction of the nitro group, or (3) by trans-esterification of a methyl or ethyl nitrobenzoate with a glycol or an acylglycol possible acylation as before, and reduction of the nitro group, or (4) by trans-esterification of a methyl or ethyl aminobenzoate with an acylglycol YCO-O-XOH or (5) by esterification of anaminobenzoic acid with an acylglycol YCOO-X-OH.

In view of their tinctorial applications, it is advantageous for the dyestuffs obtained to be in a finely divided state. This is why the dyestuffs according to the present invention are preferably previously dispersed and provided in the form of a paste or powder. This form may be realised by mixing the dyestuffs in the form of a paste with dispersing agents, and possibly with inert diluents. This mixing may be followed, if desired, by drying and grinding The dyestuffs thus treated can then be used for dye ing in a long or short bath, for foularding or printing.

Among the dispersing agents which may be used are for example, the products from the condensation of naphthalenesulphonic acids with formaldehyde, especially dinaphthylmethane-disulphonates, esters of sulphonated succinic acid, alkali metal salts of the sulphuric esters of fatty alcohols, for example sodium lauryl sulphate, lignosulphonates, soaps, alkali metal salts of the sulphuric esters of monoglycerides of fatty acids, the products obtained by condensation of the cresols with formaldehyde and naphthosulphonic acids, the condensation products of 4,4- dihydroxy-diphenylsulphone with formaldehyde and alkali metal bisulphites.

The dyeing of polyester fibres can be carried out in the presence of a carrier at temperatures ranging from 80 C. to 125 C. or without a carrier under pressure at between 100 C. and about 140 C.

They can also be foularded or printed with an aqueous dispersion of the new dyestuffs, and the impregnation obtained fixed at between 140 C. and 230 C., for example by means of steam, air or by contact with a heated surface. The range of temperature between 180 C. and 200 C. is particularly favourable since the dyestuffs diffuse rapidly into the polyester fibres and do not sublime even if the action of these high temperatures is prolonged. This enables clogging or fouling of the dyeing apparatus to be avoided.

Cellulose diacetate is preferably dyed by exhaustion at between 65 C. and 85 C. and cellulose triacetate and the polyamide fibres are preferably dyed at temperatures up to C. The most favourable range of pH is between 2 and 9 and especially between 4 and 8. The triacetate and the polyamide fibres can be foularded or printed, like the polyester fibres, with an aqueous suspension of the new dyestuffs and the impregnations obtained fixed at between C. and 210 C.

In foularding or printing, the usual thickeners may be used, for example, modified or non-modified natural products such as the alginates, crystalline gum, carob, gum tragacanth, carboxymethylcellulose, hydroxyethylcellulose, starch or synthetic products such as polyacrylic amides or polyvinyl alcohols.

The shades thus obtained are remarkably fast to thermal fixation, sublimation, creasing, combustion gases, overdyeing, dry cleaning, chlorine and wet tests, for example, Water, washing and sweat. The reserve of the natural fibres, especially of wool and cotton, and the dischargeability are good. The fastness to light is remarkable even with light shades, so that the new dyestuffs are very suitable for the production of fashion shades. The dyestuffs resist boiling and reduction at temperatures between 80 C. and 220 C. This stability is not altered by the bath ratio nor by the presence of dyeing accelerators.

The new dyestuffs can also be used for dyeing polyolefine fibres, fibres based on polymers or copolymers of acrylonitrile or based on polyvinyl derivatives.

Certain dyestuffs of Formula I lend themselves to the colouration in bulk of varnishes, oils, synthetic resins and synthetic fibres spun from their solutions in organic solvents. Some of these dyestuffs are also remarkably adapted to the dyeing of synthetic fibres modified by a metal, for example, nickel polyolefine fibres.

The invention is illustrated by, but not limited to, the following examples in which the parts are parts by weight unless the contrary is indicated.

EXAMPLE 1 205.1 parts of the potassium salt of para-nitrobenzoic acid are mixed with 120 parts of glycol chlorhydrin and the mixture is heated under reflux until condensation is complete. 196 parts of ethylene glycol p-nitrobenzoate (MP. 76-76.5 C.) are obtained which is heated under reflux in 112 parts of acetic anhydride. When the reaction is finished, the [i-acetyloxyethyl ester of the p-nitrobenzoic acid is isolated in a mixture of water and ice. It melts at 71 C. (73 C. after recrystallisation from a mixture of water and alcohol).

Analysis.-Calculated (percent): C, 52.17; H, 4.34; N, 5.53. Found (percent): C, 52.92; H, 4.67; N, 5.58.

By reduction of this ester, for example by the Bchamp method, the ,B-acetyloxyethyl ester of p-aminobenzoic acid is obtained which melts at 94 C. When recrystallised from a mixture of water and methyl alcohol, this product melts at 9697 C.

Analysis.-Calculated (percent): C, 59.19; H, 5.83; N, 6.28. Found (percent): C, 59.13; H, 6.19; N, 6.29.

EXAMPLE 2 105 parts of ethylene glycol p-nitrobenzoate obtained as in Example 1 are added to parts of xylene and 75 parts of diethylaniline. The mixture is heated to 60 C. and 83.25 parts of cinnamoyl chloride are introduced. When the reaction is finished, the mixture is run into water and the fi-cinnamoyloxyethyl ester of the p-nitrobenzoic acid is filtered off and dried. It melts at 93-94 C.

By reduction of this ester in a neutral or acid medium, the fi-cinnamoyloxyethyl ester of p-aminobenzoic acid is obtained, which when recrystallised from methyl alcohol melts at 152 C.

Analysis.-Calculated (percent): C, 69.23; H, 5.76; N, 4.48. Found (percent): C, 69.13; H, 5.44; N, 4.60.

Prepared in an identical way, the fl-benzoyloxyethyl ester of p-aminobenzoic acid melts at l34135 C.

Analysis-Calculated (percent): C, 67.36; H, 5.27; N, 4.91. Found (percent): C, 67.10; H, 5.88; N, 5.07.

EXAMPLE 3 50 parts of [4-B-hydroxyethoxycarbonyl-benzene]- 1 azo 4 -[1 phenyl 3 methyl-S hydroxy-pyrazole] are heated for 2 hours under reflux with 200 parts of acetic anhydride. A part of the acetic acid formed and the excess anhydride is driven off and the product is left to crystallise and the crystals are filtered off. The crystallisation can be accelerated by adding alcohol or petrol ether. The paste of dyestuff obtained is then mixed with a dispersing agent, for example a cresol-formaldehyde-naphtholsulphonic acid condensation product and used as such or after drying.

When applied on polyester fibres, for example by means of a dyebath at about 100 C. with the addition of a carrier, or at high temperature between 120 C. and 1.40" C. or by printing, foularding and thermal fixation, the acetyl derivative gives a yellow shade having excellent fastness to light and sublimation.

EXAMPLE 4 1115 parts of the fl-acetoyloxyethyl ester of p-aminobenzoic acid are dissolved in 1000 parts of water and 110 parts by volume of hydrochloric acid and are diazotised by adding parts of sodium nitrite. The solution of the diazo derivative is introduced into a solution of 105 parts of 1-phenyl-3-carbon-amido-5-pyrazolone in 2000 parts of water containing 120 parts of sodium car- TABLE A.Continued Example Coupling compound, D01 or D2H Shade on polyester thalene. 3-hydroxy-diphenylene'oxide Brown orange.

2-hydroxycarbazole 0. 7-hydroxy-eoumarin Yellow. l-hydroxyA-sulphena Yellow brown. 2-hydroxy-3-carhouamido-naphthalene Red orange. 2-hydroxy-N-(2-methoxy-phenyl)-3- Yellow.

carbonamido-uaphthalene. 37 6-hydroxy-indazole Yellow orange. 38 8-hydroxy-quiuoline Brown on nickel polypropylene.

On operating as in Example 4 from diazotisable bases and coupling compounds indicated in Table B below, other monoazo dyestuffs are obtained of which the shades on polyester fibres are indicated in the last column.

TABLE 13 Example Diazotisable base 30 B-Cinnamoyloxyethyl ester of p-aminobenzoic acid B-(phenylacetylocy)cthyl ester of p-aminobenzoic'acid. B-[(2, 4'-dichloro-phenoxy)-acetyloxy]ethyl ester 0 B-Benzoyloxyethyl ester of p-aminobenzoie acid B-Acryloyloxyethyl ester 01 p-arninobenzoic aei B-Acetyloxyethyl ester of m-aminohenzoic acid 'y-Acetyloxypropyl ester of p-amin0benzoic acid flAcdetyloxyethyl ester of anthranilic acid o Shade on Coupling compound, D,H or D 11 polyester l phenyl-3-methyl-5-pyraz0l0ne Do. Do. Do. Do. o. Do. N-methyl-4-hydroxy-Z-quinolone Greenish yellow. l-phenyl-Zethoxy-carbonyl-5- Yellow.

pyrazolone. l-phenyLB-carbonamido-E-pyrazolone Do.

bonate and 200 parts of sodium acetate. The dyestuff obtained is isolated in the conventional manner, mixed with a dispersing agent and if desired dried. It dyes polyester fibres a yellow shade possessing excellent general fastness, particularly to light and sublimation.

On replacing the 1-phenyl-3-carboamido-5-pyrazolone in Example 4 by the coupling compounds enumerated in the following Table A other monoazo dyestuifs are obtained of which the shade on polyester fibres is indicated in the third column.

TABLE A Example Coupling compound, D1H or DzH Shade on polyester 5 1-phenyl3-rnethyl5-pyrazo1one Yellow. 6 2,6-dichloro-1-phenyl-3-methyl-5- Greeiush yellow.

pyrazolone. 7 3-methy1-5pyrazolone Do. 8 3-su1phonamido-l-phenyl-3-methyl-5- Yellow.

pyrazolone. 0 3-nitro-1-phenyl-3-methyl-fi-pyrazolone. Do. l-hydroxyeth yl-3-rnethyl-5-pyrazolone Do. 11 l-phenyl-3-N-ethylcarbonamido 5- Do.

pyrazolone. 12 2,4-dihydroxy-quinoline Greenish yellow. 13 N-hydroxyethyll-hydroxy-2-quinolone Do. 14 N-methyl-4-hydroxy-Z-quinolone Do. 15- N-ethyl-N-cyanoethyl-aniline Reddlsh yellow. 16 Ethyl ester of N-ethyl-N-(3-methyl- Yellow orange.

phenyl) aminopropionic acid. 17 N,N-bis-(cyanoethyl)-metatoluidine Yellow. 18 N-methyl-N-cyanoethyl-metatoluidine- Yellow orange. 19 4-diiuethylamino-2-acetylaminobenzene Orange.

EXAMPLE 49 111.5 parts of the fl-acetyloxy-ethyl ester of p-aminobenzoic acid are diazotised as in Example 4 and the solution of the diazo derivative is introduced into a solution of 61.5 parts of m-anisidine dissolved in parts of 30% hydrochloric acid and 1000 parts of water. The coupling is finished by the addition of 250 parts of sodium acetate, the mixture is filtered and the precipitate obtained is made into a paste in 5000 parts of water, 200 parts of 30% hydrochloric acid are added and the amino-azo compound is diazotised by means of 35 parts of sodium nitrite.

The solution of the diazo derivative is introduced into 87 parts of 1-phenyl-3-methyl-5-pyrazolone dissolved in 2000 parts of Water by means of 20 parts of caustic soda and 200 parts of sodium carbonate. The dyestuff obtained is isolated by filtration and mixed with a dispersing agent and dried if desired. It dyes polyester or triacetate fibres a reddish orange shade possessing excellent general fastness, especially to light and sublimation.

Table C below groups together other examples of disazo dyestuffs prepared as in Example 49 by diazotising the B- acetyloxyethyl ester of p-aminobenzoic acid, coupling with an amino coupling compound H-BNH diazotising the monoazo dyestuff and coupling with a coupling compound DIH 0r DZH.

TABLE O Shade on Example 1st coupling compound HB-NHZ Final coupling compound D 11 or D H polyester 50 m-Anisidino l-phenyl-3-ethoxycarbonyl-5-pyrazolone Scarlet. 5L. do l-phenyl-3-carbonamido-5-pyrazolone Do.

l-phenyl-3-eth0xycarbonyl-b-pyrazolone l-phenyl-3-carbonamido-5-pyrazolonc. 2-hydroxy-B-carbonamido-toluenel-phenyl-3-methyl-5-pyrazolone. 0.

Phenol Yellow orange.

2-hydroxy-3-carbonamido-naphthalcnc. Bluish rod. 1-l1ydroxy 3-carbonamido-tolucne Yellow. 59.- o N-111ethyl-M1ydroxy-2-quinolone Orange. 60.- 2-111Gtl1OXy-5'Ill0thy1-al1i1il10 Phenol 0. 6L. 2,5-dimethoxy-aniline l-phenyl-3-mcthyl-5-pyrazolone. Red.

o Ph 01 Scarlet. 63 a-Nalphthylamine. Brown orange y aNapl1thol 2-hydroxy-3-carbonamido-toluene. Orange.

do N-acetyl-m-phenylcno-diamino. A. l-phenyl-3-carbonamido-5-pyrazolone Scarlet.

EXAMPLE 68 EXAMPLE 70 An ethylene glycol polyterephthalate fabric is impreg- 100 parts of a cellulose triacetate fabric is introduced nated by foularding with a bath which contains per 1000 at 6070 C. in a dyebath of 3000 parts which contains parts, 9.0 parts of the dyestutf obtained in Example 14, 1 part of the dyestufif described in Example 4 and 15 parts 0.5 part of a polyglycol ether of oleyl alcohol, 1.5 parts of o-phenyl-phenol. The bath is brought to the boil in a of a polyacrylic amide and the quantity of water necesperiod of half an hour and dyeing is continued at the boil sary to make up to 1000 parts. After drying, the fabric for an hour. After finishing treatment, a yellow shade of is subjected to thermal fixation for 1 minute at 200 C. excellent fastness to light and sublimation is obtained. and then to a reducing treatment with sodium dithionite. We claim: A greenish yellow shade having good fastness to light and 1. A water-insoluble dyestulf free from solubilising acid sublimation is obtained. groups and having one of the formulae V no I N or n- N=NB-N=N l N w COO-XO-CO--Y D1 V Q N Y-CO-0XOG0'-N=N B-N=N 1 EXAMPLE 69 in which 111 represents number 0 or 1, X represents the ethylene or propylene, Y is methyl, vinyl, phenyl, benzyl, A11 ylene g y Polyterephthalatfi fabric is Printed styryl or 2,4-dichlorophenoxymethyl, B represents p-phenwith a printing paste which contains, per 1000 parts, 20 ylene or p-naphthylene or p-phenylene substituted by one parts of the dyestuif described in Example 51, 150 parts acetylamino or by one or two methyl or methoxy, D is of the sodium salt of a sulphonated castor oil, 600 parts methyl, Carbonamido or cthoxycarbonyl, D is methyl, of a thickener and 250 parts of water. After drying, the carbonamido or ethylaminocarbonyl, V is hydrogen or fabric is subjected to thermal fixation for one minute at chlorine, and W is hydrogen, chlorine, nitro or sulphon- 200 C., and then to a reducing treatment. A scarlet shade amido. having good fastness to light and sublimation is obtained. 2. The dyestulf of the formula:

3. The dyestulf of the formula (References on following page) 9 10 References Cited 3,324,105 6/1967 Hanke et a1. 260163 X 3,325,469 6/ 1967 Berrie et a1. 260-163 X UNITED STATES PATENTS 3,483,182 12/1969 Sugiyama et a1. 260163 6/1936 Raeck 61 a1. 260 155 5/1942 Felix 61 al 260--163 5 FLOYD D. HIGEL, Primary Examiner 8/1952 Salvin 618.1. 260187 7/1963 Fishweik et a1. 260-2071 -R 6/1965 Skoultchi et a1. 260207.1 x

106-288 Q; 117-138.8 R, 138.8 B; 260-152, 155, 156, Sk l l chl 012 l 260-1071 X 157, 160, 162, 174, 178, 185, 187, 197, 206, 207, 207.1, Monagle 260--157 10 310 A, 471 R 

